Process for breaking petroleum emulsions employing certain polyepoxide treated amine-modified thermoplastic phenol-aldehyde resins



J LfJ- United States TREATED -MODIFIED THERMOPLASTIC PHENOL-ALDEHYDERESINS Melvin De Groote, University City, and Kwan-Ting Sheri,Brentwood, M0,, assignors to Petrolite Corporation, Wilmington, DeL, acorporation of Delaware No Drawing. Application February 24, 1953,Serial No. 338,574

20 Claims. (Cl. 252-338) The present invention is a continuation-in-partof our co-p'e'nding application, Serial No. 305,079, filed August 18,1952, now abandoned.

The present invention is concerned with demulsification which involvesthe use of certain polyepoxide-treated amine-modified thermoplasticphenol-aldehyde resins for the resolution of petroleum emulsions. Morespecifically, the invention of the present application relates to thebreaking of emulsions of the water-in-oil type characterized bysubjecting the emulsion to the action of a demulsifier includingproducts obtained by the method of first condensing certainphenol-aldehyde resins, hereinafter described in detail, with a basichydroxylated secondary monoamine, having not more than 32 carbon atomsin any group attached to the amino nitrogen atom, and formaldehyde,which condensation is followed by reaction of the resin condensate withcertain phenolic polyepoxides, also hereinafter described in detail, andcogenerically associated compounds formed in the preparation of thep'olyepoxides. I

In preparing diepoxides or the low molal .polymers one does usuallyobtain cogeneric materials which may include monoepoxides. However, thecogeneric mixture is invariably characterized by the fact that there ison "the average, based on the molecular weight, of course, more than oneepoxide group per molecule.

A more limited aspect of the invention is represented by the use of thereaction product of (A) an aminemodified phenol-aldehyde resincondensate as described, and (B) a member of the class consisting of (1)compounds of the following formula and (2) cogene'rically associatedcompounds formed. in the preparation of (1) preceding.

2,771,436 Patented Nov, 2 0,. 1956 compounds be employed or elsecompounds where the divalent link is obtained by the removal of. acarbonyl oxygen atom as derived from a lietone or aldehyde.

If it were not for the expense'involved in preparing and purifying themonomer we would prefer it to any other form, i. e., in preference tothe polymer or mixture of polymer and monomer. v

Stated another way, we would prefer to use materials of the kinddescribed, for example, in .Patent 2,530,353, dated November 14, 1950Said ,pateut'describes compounds having the general formula,

ice

I wherein R is an aliphatic. hydrocarbon bridge, eachin independentlyhas'one of the values O'a'nd 1, a'nd'X is an alkyl radical containingfrom 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far aspolyepoxide goes is as follows:

U. S. Patent No. Dated Inventor 2,122,958 July 5,1939 Schafe'r.2,139,766 December 13, 1938.-- Mikeska et al. 2,174,248 September-26,1939.... Do. 2,195,539 April '2, 1940. Do. 2,207,719 .luly 16,-1940Cohen-6t 8.1 2,244,021 June 3, 1941- Rosen et 81 2,246,321 Julie 17,1941 osen. 2,285,563 .lt111e9,'1942r.-. Britton-eflal. 2,331,448 October12,1843 Winnmg eta1, 2 ;g130,002 November 4, 1947-- 2,457,329 December28, 1948 2,462,047 February 15, 1 949 Wyler. 2,462,048.. February 151949 D 2,482,748 September-917, 1949-. i 2,488,134. November 15, 194 llreslia et 21 503,196.. April 4,19 Dietzler et a1 2,504,064.. April 11,1950 Book'e't bl 2,506,486.. May 2, 1950 Bender at al 2,515,906.. In'13, 1950 Stevens et a1. 2,515,907.. July 18, 1950 r 0. 2,515,9 July 18,1950 Do.

526,545 Octobe'r17, 1950-... Dietzlr. 530,353. November 1 1, 1950Havens. 2,564,191 August 14, 1951 De G-roote et 51 2,575,558.. November20 195 Newey et a1. 2;5s1,4 January 8, 1952.- Z'eeh. 2,581,919. January8 1952. Albert.

Greenlee.

2,582,985.: January 22, 1952 The compounds having two oxira'ne rings andemployed forcomb'in'ation with the reactive amine-modifiedphenolaldehyde resin condensates as herein described are compounds ofthe following formula and cogen'erically associated compounds formed intheir preparation:

It so happens that the bulk of information concerned with thepreparation of compounds having two oxirane rings appears in the patentliterature and for the most part in the recent patent literature. Thus,in the subsequent text, there are numerous references tosuch patents forpurpose of supplying information and also for purpose of brevity.

Notwithstanding the fact that subsequent data will 'be presented inconsiderable detail, yet the description becomes somewhat involved andcertain facts should be kept in mind. The epoxides, and particularly thediepoxides may have no connecting bridge between the phenolic nuclei asin the case of a diphenyl derivative or may have a variety of connectingbridges, i. e., divalent linking radicals. Our preference is that eitherdiphenyl 'in which R represents a divalent radical selected fromthe'clas's 'o'fk'etone residues formed by theelimination of the ke'tonicoxygen atom and aldehyde residues obtained by the elimination of thealdehyde oxygen atom, the divalen'fradical 7 0 *monosulfide radical thedivalent radical in which R, R" and R represent amember of the class ofhydrogen and hydrocarbon substituents of the aromatic nucleus, saidsubstituent member having not over 18 carbon atoms; n represents aninteger selected from the class of zero and l, and n represents a wholenumber not greater than 3. The above mentioned compounds and thosecogenerically associated compounds formed in their preparation arethermoplastic and organic solvent-soluble. Reference to beingthermoplastic characterizes them as being liquidsat ordinary temperatureor readily convertible to liquids by merely heating below the point ofpyrolysis and thus differentiates them from infusible epoxide derivativecan combine with a sulfonamide resin.

The intention in said U. S. Patent 2,494,295,"of course,

reactive hydroxyl groups which are part of the phenolic nuclei and theremay be present reactive hydrogen atoms attached to a nitrogen atom, oran oxygen atom, depending on the presence of a hydroxylated group orsecondary amino group.

To illustrate the products which represent the subject 7 matter of thepresent invention reference will be made to a reaction involving a moleof the oxyalkylating agent, i. e., the compound having two oxirane ringsand a condensate. Proceeding with the example previously described it isobvious the reaction ratio of two moles of the' amine condensate to onemole of the oxyalkylating agent gives a product which may be indicated.as follows:

condensate) resins. Reference to being soluble in an organic solventmeans any of the usual organic solvents, such as alcohols, ketones,esters, ethers, mixed solvents, etc. Reference to solubility is merelyto differentiate from a reactant which is not soluble and might be notonly insoluble but also infusible. Furthermore, solubility is a factorinsofar that it is sometimes desirable to dilute the compound containingthe epoxy rings before reacting with amine. In such instances, ofcourse, the solvent selected would have to be one which is notsusceptible to oxyalkylation, as for example, kerosene, benzene,toluene, dioxane,

' various ketones, chlorinated solvents, dibutyl ether, di-

hexyl ether, ethyleneglycol diethylether, diethyle'neglyco diethylether,and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The1,2-epoxy ring is sometimes referred to as the oxirane ring todistinguish it from other epoxy rings. Hereinafter the word epoxy unlessindicated otherwise, will be used to meanthe oxirane ring, i. e., the1,2-epoxy ring. Furthermore, where a compound has two or more oxiranerings they will be referred to as polyepoxides. They usually represent,of course, 1,2-epoxide rings or oxirane rings in the alpha-omegaposition. This is a departure, of course, from the standpoint ofstrictly formal nomenclature as in the example of the simplest diepoxidewhich contains at least 4 carbon atoms and is formally described as1,2-epoxy-3,4-epoxybutane (1,2-3,4 diepoxybutane). 1

It well may be that even though the previously suggested formularepresents the principal component, or

components, of the resultant or reaction product described in theprevious text, it maybe important to note that somewhat similarcompounds, generally of much higher molecular weight, have beendescribed as complex resinous epoxides which are polyether derivativesof polyhydric phenols containing an average of more than one epoxidegroup per molecule and free from functional groups other than epoxideand hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10,1950, to Greenlee. The compounds here included are limited to themonomers or the low molal members of such series and generally containtwo epoxide rings per molecule and may be entirely free from a hydroxylgroup. This is important because the instant inventionis directedtowards products which are'not insoluble resins and have certainsolubility characteristics not inherent in the usual thermosettingresins." Note, for example, that said U. 5..

Patent No. 2,494,295 describes products wherein the for purpose ofresolution. of petroleum emulsions of the (condensate in which thevarious characters have their previous significance and thecharacterization condensate is simply an abbreviation for the'condensatewhich is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is notlimited to an organic solvent but may include water, or for that matter,a solution of water containing an acid 'such as hydrochloric acid,acetic acid, hydroxyacetic acid, etc. Inother words, the nitrogen groupspresent, whether two or more, may or may not be significantly basic andit is immaterial whether aqueous solubility represents an anh yd ro baseor the free base -(co'mbination with water) or a salt form such as theacetate, chloride, etc. The purpose in this instance is to dilferentiatefrom insoluble resinous materials, particularly' those resulting fromgelation or cross-linking. Not only does this property serve todifferentiate from instances-where an insoluble material is desired, butalso serves to emphasize the fact that'in many instances the preferredcompounds have distinct water-solubility or, are

distinctly dispersible in 5% gluconic acid. 7 For instance,

the products freed from any solvent can be shaken with 5 to 20 timestheir weight of distilled water at ordinary temperature and show atleast some tendency towards being self-dispersing. The solvent which isgenerally tried is xylene. If xylene alone does not serve then a mixtureof xylene and methanol, for instance, 80 parts of xylene and 20 parts ofmethanol, or 70 parts of xylene and 30 parts of methanol can be used.Sometimes it isdesirable to add a small amount of acetone to thexylene-methanol mixture, for instance, 5% to 10% of acetone.

The polyepoxide treated condensates obtained in the manner describedare, in turn, oxyalkylation-susceptible and valuablederivatives can-beobtained by further reaction with ethylene oxide, propylene oxide,ethylene imine,

etc. c

Similarly, the polyepoxide-derived .compounds can be reacted with aproduct havingbotha nitrogen group and a 1,2:epoxy group, suchas.3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093 datedAugust 22, 1950, to Gross. a

As far as the use of the herein described products goes water-in-oiltype, we particularly prefer to use those which as such or in the formof the free base orhydrate, i. e.,

combination with water or particularly in the form of a.

low molal organic acid salt such as the gluconates or the acetate orhydroxy, acetate, have sufficientlyhydrophi-le character to at leastmeet the test set forth in U. S; Patent No. 2,499,368, dated March 7,1950,10 De Groote et al. In said patent such test for emulsificationusing. a water.- insoluble solvent, generally xylene, is described as anindex of surface activity.

In the. present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

For. purpose of convenience what is said hereinafter will be dividedinto eight parts with Part 3, in turn, being divided into threesubdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide andparticularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxidepreparation;

Part 3, Subdivision A, is concerned with the preparation of. monomericdiepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molalpolymeric exopides or mixtures containing low molal polymeric epoxidesas well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolicreactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated secondary amineswhich may be employed in the preparation of the herein-described aminemodified resins;

Part 6 is concerned with reactions involving the resin, the amine, andformaldehyde to produce specific products or compounds which are thensubjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding typesof materials and examples obtained by such reaction. Generally speaking,this involves nothing more than a reaction between 2 moles of apreviously prepared amine-modified phenol-aldehyde resin condensate asdescribed, and one mole of a polyepoxide so as to yield a new and largerresin molecule, or comparable product;

Part 8 is concerned with the resolution fo petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of.polyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. If such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solvent-soluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in whichthere are more than two epoxidegroups per molecule. Thus,

o nr cti a rp m ee hat; is said h eina er is; larg y limited topolyepoxidesin the form of, diepoxides,

As has been pointed. out previously one of the re.- actants employed; isa diepoxide reactant; It is, generally obtained from phenol (hydroxy benzene) or substituted phenol. The ordinary, or: conventional manufacture;of the epoxides usually results in the formation of a co: genericmixture explained subsequently. Preparation of the monomer or separationof; the monomer from the remaining mass of the co-generic mixture is.usually; ex,- pensive. If monomers were available commercially at at lowcost, or if they could be. prepared without added expense.forseparation, our. preference would be to use the monomer. Certain,monomers have. been prepared and; described in the. literature and willbe referredto subsequently. However, from a, practical standpoint. onemust weigh the advantage, ifany, that the monomer has over other lowmolal polymers from a cost=standpoint;

thus, we have found that one; might as, Well attempt to prepare amonomer. and fully recognize that there. mav be present, and probablyinvariably are present, othe low molal polymers in comparatively smallamounts. Thus, the materials which are most apt to be used. for P a ic lrea n e i he m m s 'With me. al amounts of polymers. present or mixtureswhich have a suh tan i a ount of p mer q n ee he mi fill l can be.prepared free from mourners and still be satisfactory. Briefly, then,our preference is to use the monomer or the monomer with the minimumamount of higher polymers,

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be directly united, or united through a variety ofdivalent radicals. Actually, it isjour preference. to use thosewhich arecommercially available andfor most practical purposes. it meansinstances where the phenolic nuclei are either united directly withoutany intervening linking radical, or else united by a ketone. residue or,formaldehyde residue.

The commercial bis-phenols available now in the open 7 market illustrateone class. The diphenyl derivatives illustrate a second class, and thematerials obtained by reacting substituted monofunctional phenols withan aldehyde illustrate the third class. All the various known classesmay be used but our preference rests with these classes due to theiravailability and ease of preparation, and also due to the fact that thecost is lower than in q h rera s Although the diepoxide reactants can beproduced in more thanone way, as pointed out elsewhere, ourpreference isto produce them by means of the epichlorohydrin reaction v referred toin detail subsequently. A

One epoxide which can be purchased in the open market'and containson lya modest amount of polymers corresponds to thederivative of bis-phenoLA.It can be used as such, or the monomer can be separatedby an added stepwhich involves additional expense. This compound of the followingstructure is preferred as the epoxide reactant and will be. usedfor.illustration repeatedly with .the full understanding that any of theother epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higher.polymers are satisfactory. The formula. for this. compoundis Referencehas just been made to bis-phenol A and a suitable epoxide derivedtherefrom. Bis-phenol A is i drox e phe y d methrl me han with, the ,4isomar r ouiuat a au h h ss r. u t t w h and 4,2 isomers being presept.It is immaterial which one of these isomersis used andthecommerciallyavailable mixture is entirely satisfactory.-

. 7 Attention is again directed to theffact that in the 'instant part,to wit, Part- 1,- and in succeeding parts, the

7 text is concerned. almost entirely with epoxides'in which classes ofepoxide reactants.

If sulfur-containing compounds are' prepared they should be freedfrom-impurities with considerable care for the reason that any time thata low-molal sulfurcontaining compoundcan react with 'epichlorohydrinthere maybe formed a lay-product in which the chlorine happened tobe'partic'ularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall concentration. I e r a PART 2 be derived by more than one methodas, for example, the use of epichlorohydrin or glycerol dichlorohydrin.If a product such as bis-phenol A is employed the ultimate compound inmonomeric form employed as a reactant in the present invention hasthe'following structure:

Treatment with epichlorohydrinpfor example, does not yield this productinitially but there is an intermediate produced which can be indicatedby the following structure: 5

Treatment with alkali, of course, forms the epoxy ring. A number ofproblems are involved in attempting to produce this compound free fromcogeneric materials of related composition. The difliculty stems from anumber of sources and a few of the more important ones are as follows: ig i r 1) The closing of the epoxy ring involves the" use of caustic sodaor the like which, in turn, is an effective catalyst in causing the ringto open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that oneobtains a product in which there is only one epoxide ring and there may,as a matter of fact, be more than one hydroxyl radical as illustrated bythe following compounds: 1 V

' (2) Even if one starts with the reactants in the preferred ratio, towit, two parts of epichlorohydrin to one part of bis-phenol A, they donot necessarily so react and as a result one may obtain products inwhichmore than two epichlorohydrinresidues become attached to a Thepolyepoxides and particularly the diepoxides can I produce a solidpolymer.

Water, forms cyclic polymers. Indeed, ethylene oxide can This samereaction can, and at times apparently does, take place in connectionwith componds having one, or in the present instance, two substitutedoxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways itis easier to produce a polymer, particularly a mixture of the monomer,dimer and trimer, than it is to produce the monomer alone.

i (4) As has been pointed out previously, monoepoxides may be presentand, indeed, are almost invariably and inevitably present when oneattempts to produce poly-v epoxides, and particularly diepcxides. Thereason is the one which has been indicated previously, together with thefact that in the ordinary course of reaction a diepoxide,

may react with a mole of bis-phenol A to give a monoepoxy structure.Indeed, in the subsequent text immediately following reference is madeto the dimers, trimers and tetramers in which two epoxide groups arepresent. Needless to say,fcompounds can be formed which correspondinevery respect except that one terminal'epoxide group is absent and inits place is a group having one chlorine atom and one hydroxyl group, orelse What has been said in regard to the theoretical aspect particularlysubdivisions Aand B. There can be no clear line between the theoreticalaspect and'actual preparative steps. However, in order to summarize orillustrate what example is It is obvious that two moles of such materialcombine readily with one mole of bis-phenol A,

to produce the product which'is one step further along, 7

.at-least, towards polymerization. In otherwords, one prior exampleshows' the reaction product obtained from "one mole of the bisphenolA'Qand two moles of epichlorohydrin. This product in turn wouldrepresent three moles of bisphe'nol A and four moles of.epichlorohydrin. For purpose of brevity, without going any further, the

next formula is in, essence onejwhich, perhaps in an air-1,436

For the purpose of the instant invention, n may ,re pige sent a numberincluding zero, and at the most a low number such as 1, 2 or 3.limitation does not exist actual etforts to obtain resins asdifierentiated from the herein described soluble materials. It isquiteprobable that in the resinous products as marketed tor coating usethe value of n is usually substantially higher. Note again what has beensaid previously that any formula is, at best, an over-simplification, orat the most represents perhaps only the more important or principalconstituent or constituents. These materials may vary from simple At theexp nse of r pe n o what sm ared pre ilO ously, it may be well to recallthat these materials may groups other than epoxide and hydroxyl groups.The

former are here included, but thev latter, i. e., highly resinous orinsoluble types, are not.

in summary then in -light of what *has been said, com pounds suitable-for reaction with amines may be sum:

non-resinous to complex. resinous epoxides which are marized by thefollowing iormuia:

polyether derivatives of polyhydric phenols containing an average ofmore than one epoxide group per molecule and free from functional groupsother than epoxide andhydroxyl groups. 7

Referring now to "What has ';been said previously, to 'wit,

compounds having both an epoxy ring or the equivalene and also ahydroxyl group, one need go no further than to consider the reactionproduct of and bisphenol A in a mole-for-mole ratio, since the initialreactant would yield a product having an mnreacted epoxy ring and tworeactive hydroxyl radicals. Referring again a to a previous formula,consider an example where two or 9; greater simplicity the formula couldbe restated hu Ea J 2 th in which the various characters have theirprior significance and in which R10 is the divalent radical obtained bythe elimination of 'a hydroxyl hydrogen atom and a nuclear hydrogen atomfrom the phenol in-which -R,-R", and 'R represent a member of the classconsisting of hydrogen and hydrocarbon substituents of the aromaticnucleus, said;substituent member having not moles of bisphenol A havebeen reacted with 3 moles of over 18 carbon atoms; 1 represents aninteger selected epichlorohydrin. The simplest compound formed would bethus:

Such zazeompound is comparable to other compounds hav ing both "thehydroxyl :and epoxy ring such as 9,l 0-epoxy octadecanol. The ease withwhich this type of compound 5 polymerizes is pointed outhy .U S .PatentNo. 2,457,329 dated December 28, 1948, to Swern et al.

The same difiiculty which involves the tendency" to polymerize on thepart of compounds having a reactive ring and a hydroxyl radical may :beillustrated by cognpounds where, instead of the oxiranering (1,2-epoxyring) there is present a 1,3-epoxy ring. Such compounds are derivativesof trimethylene oxide rather than ethylene oxide. See U. S. Patents Nos.2,462,047 and 2,462,048, both dated February 15, 1949, to Wyler.

from the class of zero and '1', and n' represents a whole number notgreater than 3.

PART 5 Subdivision A The preparations of the diepoxy derivatives of thediphenols which are sometiues referred to as diglycidyl ethers, havebeen described in a number of patents. For convenience, reference willbe made to two only, to wit, aforementioned U. S. Patent 2,506,486, andaforementioned U. S. Patent No. 2,530,353.

Purely by twayiofzillustration, .the following diepoxides, or diglycidylothers as they are sometimes termed, are included for purpose ofillustration. These particular compounds are described in the twopatents just mentioned.

awe-3e TABLE I Ex- I Patent ample Diphenol Diglycidyl ether refernumberence CHKCuHiOH); Di epoxypropoxyphenyhmethane 2. 506, 486 CH.OH(OH4OH)1.DigepoxyproDomhenyDmethylmethane. 2. 506, 486 (CHzhC (CH4OH):.. 2, 506,486 C: a (CH: uH40H)2 Di(epoxypropoxyphenyl)ethylmethylmethane 2, 506,486 :H|)z0(CeH40H)2 EepoxypropoxyphenyDdiethy methane 2, 506. 486 v CHaCCaH'I) (CqH4OHh. Di epoxypropoxyphenyhmethy propylmethane 2, 506, 48601m: (0511) (C6H40H)2... Di(epoxypropoxyphenyl)methy phenylmethane. 2,506, 486 CgH C(CnH5)(CnH4OH)1.. Di(epoxypropoxyphcnyl)ethylpaenylmethane- 2, 506, 486 C8H'IC(O6HI)C6HAOH)L.Di(epoxypropoxyphenyl)propyl henylmethane 2, 506; 486 C|HC(C9H5)CH4OH):.. Di(epoxypropoxyphenyl)butylp enylmethane.-.. 2, 506, 486(CHaCeH4)GH(CaH40H)L.. Di(epoxypropoxyphenyl)tolylmethane 2, 506, 486(CH O H4) 0 (CH3) (003401501. Di(epoxypropoxyphenyl) tolylmethylmethanm-2, 506, 486 ihydroxyrdiphenyl 4,4-bis(2,3-epoxypropoxy)diphenyl 2, 530,353 (CH1)O(C4H .O H OH) 2,2-bis(4-(2,3-epoxypropoxy)Z-tertiarybutylphenyDpropane.-- 2, 530, 353

Subdivision B As to'the preparation of low-molal polymeric epoxides ormixtures reference is made to numerous patents and particularly theaforementioned U. S. Patents Nos. 2,575,558 and 2,582,985.

In light of the aforementioned U. S. Patent No. 2,575,- 558, thefollowing examples can be specified by reference to the formula thereinprovided one still bears in mind' that it is in essence anover-simplification.

* .TABLEII C 7 0-0- -ORr-[R],.R;0-C-( JC -0R1[R],.R1O-0OC H; H H: H: H2H2 H H:

(in which the characters have their previous significance) Example R O-from HRrOH -R n 1: Remarks number B1 Hydroxy benzene OH; 1 0,1,2 Phenolknown as bis-phenol A. Low polymeric mixture about %,or more where n'=0,remainder largely where r 'n=l, some where 'n=2. CH:

B2 ..d0 CH; 1 0,1,2 Phenolknown as bis-phenol B. Seenote regardlng Blabove.

+11: 1 7 CHI 7 B3 Orthobutylphenol 0H; 1 0, 1, 2 Even though 1L ispreferably 0, yet the l I usual reaction product might well eon- --Ctain materials where n isl, or to a l lesser degree 2. CH: 1

B4 Orthoamylphenol n'. 7 CH; 1 0,1,2 Do.

OH; I

135 Orthooctylphenol tilH; v1 0,1,2 Do.

BB orthononylphenolur EH; 1 0,1,2 Do. 7

B7 Orthododecylphenoluunn- $11; 1 0,1,2 Do.

B8--. Metacresol CH; 1 0,1,2 See prior note. This phenol used as 1initial material is known as bis-phenol C. For other suitablebis-phenols see. a U. 5. Patent 2,564,191. 4 139 .do .Q; EH; 1 o, 1, 2See prior note.

B10 Dibutyl (ortho-para) phenol. 1 0,1,2 Do.

TABLE II (continued) 1 J I Example R Ir0m HIhOH R n n Remarks number B11Diamyl (ortho-para) phenolg l 0, 1, 2 Bee prior note.

E1 2... i Dioetyl '(ortho-panDphenoL; 1g 1' 0,1,2 -Do.

B13 Dinonyl (ortho-para) phenol. 1 0,1, 2 Do.

B14 Dlamyl (or'tho-para) phenol i 1 0, 1, 2 DO.

I OH:

B16 do 161 1 0, 1, 2 Do.

.I V CQHB 316..--.. Hydroxy benzene .1 l) 1 0,1,2 Do.

Dlamy'lphenollortho-para)- -;s-=s- 1 0,1, Do.

BI8 -do --S- 1 0,1,2 Do. B19 Dibutyl phenol (orthopara). .1 0,1,2 Do.

' H H I i 1320.--.-. -.--do H g i 1 0,1,2 Do.

H H p B21 Dinonyl'phenol(ortho-pera)- B22 Hydroxy benzene 1 0,=1,2 D0.

"1130 None..-. 0,1,2 Do. p 1324...-.. Ortho-isopropyl pheno1 C H; i 0,1, 2 See prior note. As to preparatiomof-gylsopropylidenebis-(2-isopropylphenol) see U. 8. Patent No. 2,482,758, flatten Sept.27, 1949, to Dietzler. 16H; I 1

B25 Para-octyl phenol CH;SCH: 1 0, 1, 2 See prior note. ('Astopreparatlonrofthe phenol sulfide see U. 5. Patent No, 2,488,134, datedNov. 15, 1949, to V I I Mikeska et 81.) B26. Hydroxybenzene OH; 1 0,1,2See prior note. (As to preparationwf the phenol sulfide see U. 8. PatentNo. 526,345.)

I CzHi Su'bdivisionC The prior "examples have been limitedrlargely-rtothose in which there is no divalent linking radical, as 'in the case ofdiphenyl compounds, or where the linking radical is derived fromake'tone or aldehyde, particularly a ketone. Needless to 'say, the sameprocedure is employed'in converting diphenyl into 'a dig'lycidyl ether'11:- gariiless of the nature of the bond between the two phenolicnuclei. .For purpose of illustration attention is directed .to numerousother diphenols which can be readily :converted to a suitablepolyepoxide, and particularly diepoxide, reactant.

previously pointed out the initial phenol :may he substituted, and thesubstituent rgroupsin turn :may he :a cyclic group'such as the 'phenylgroup 1 or cyclohexyl group as in the instance of 'cyclohexylphenol -or-phenylphenl; Such subst ituents are usually in the ortho'position "andmay be illustrated by a phenol ,of the following composition:

Other samples include:

OH; OH:

wherein R1 is a substituent selected from the class con 3 sisting ofsecondary butyl and tertiary butyl groups and R2 is a substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl,and alkaryl groups, and

wherein said alkyl group contains at least 3 carbon atoms. See U. S.Patent No. 2,515,907.

11(0 CIHOlO O(O:H40)0H 05111160 v-OCIE:

ClHu CsHil in which the C5Hu groups are secondary amyl groups.

See U. S. Patent No. 2,504,064.

H" Cl is HO OH See U. S. Patent No. 2,285,563.

H C H C CHr--CH, I

'oHr-o See U. S. Patent No. 2,503,196.

OH; i Q

G s CH: wherein R1 is 'a substituent selected from the class consistingof secondary butyl and tertiary butyl groups and R2 is 60 a substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl,and alkaryl groups. See U. S. Patent No. 2,515,960.

on=on 0 I V on o=0H on s u. s. are... No. 2515.902.

' -16 As to sulfides,-th e following compound is of interest:

" 05H CsHu V V T i oH- OH See U. S. Patent No. 2,331,448. As; todescriptions of various suitablephenol sulfides; reference is made tothe following patents: U. S. Patents Nos. 2,246,321, 2,207,719,2,174,248, 2,139,766, 2,244,- 021, and 2,195,539

As to sulfones, see U. S. Patent No. 2,122,958. As to suitable compoundsobtained by the use of form-. "aldehyde or some other aldehyde,particularlyhom pounds such as v Alkyl R Alkyl Alkyl v Alkyl in which R5is a methylene radical, or a substituted methylene radical whichrepresents the residue of an aldehyde and is preferably theunsubstituted methylene radical de-. rived from formaldehyde. See U. S.Patent No. 2,430,-

' See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol)sulfides which include the monosulfides, the disulfides, and thepolysulfides. The following formula represents the variaus di'c'resolsulfides 'or this invention:

= i r 0H OH:

' in which R1 andRz are alkyl groups, the sum of whose carbonatomsequals 6 to about 20, and R1 and R2 each 40 preferably contain 3 toabout 10 carbon atoms, and x is 1 to 4. The term sulfides as used inthis text, therefore,

water-insoluble resin polymers of a composition approximated in anidealized form by the formula OH OH OH s a H H R R n R In the aboveformula n represents a small whole number varying from 1 to 6, 7 or 8,or more, up to probably 10 or 12 units, particularly when the resin issubjected to heating under a vacuum as described in the literature. Alimited. sub-genus is 'in the instance of low molecular weight polymerswhere, the total number of phenol'nuclei variesfrom 3 to 6, i. e., itvaries from 1 to 4; R represents an aliphatic hydrocarbon substituent,generally an alkyl radical having from 4 to 15 carbon atoms, such as abutyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge,radical is'shown as being derived from formalde hyde it may, 'of course,be derived from any other reactive aldehydehaving 8 carbon atoms'orless. i Because a resin is organic solvent-soluble does not mean it is'necessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance paraphenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane ordiethyleneglycol diethylether.

syn-1,436

'S ometirnes-a'mixmre of the two solvents' foxygena'ted andnonoxygenated') will serve. see lixample 9a of U. "S. Patent No.2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. 8. Patent .No. 2,499,368, dated March 7, 1950,to De Groote and Keiser. In said patent there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resins havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule. These resins are difunctional onlyin regard to methylol-forming reactivity, are derived by reactionbetween a difunctional monohydric phenol and an aldehyde having not over8 carbon atoms and reactive toward said phenol and are formed in thesubstantial absence of trifunctional' phenols. The phenol is of theformula The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain ahundred percent yield for obvious reasons. Certain side reactions maytake place. For instance, 2 moles of amine may combine with one mole ofthe aldehyde or only one mole of the amine may combinewith' the resinmolecule, or even to a very slight extent, if at all, 2 resin units maycombine without any amine in the reaction product, as indicated in thefollowing formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldeparticular aldehyde employed to form the resin.

8- hyde or butyraldehyd'e. Theresin'unit may be exemplified thus: 7

in which'R is the divalent radical obtained from the For reasons whichare obvious the condensation product ob tained appears to "be describedbest'in terms of "the method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst'having neither 'acid nor'basi'c properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid :should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base. .be neutralized although we have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount" of a free base. The amount may be as small as a 200th of apercent and as much as a few lOths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and .pentamer' present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the. actual manufaotureof the resins we found no reason for usingother than thosewhich are lowest in price and most readily available.commercially. For pur poses, of convenience suitable resins arecharacterized-in the following table: 'l

TABLE III :Mol. wt.

Ex- R oi resin; ample R Position derived n molecule number or R from-(based.

on n+2) j 1a Phenyl Party... 3.5 992.5

2a Tertiary butyl ,do. 3.5 882.6

Secondary butyl. Ortho.-. 3. 5 882. 5 Cycle-beryl Para..." -3. 5 1,025.5 Tertiary amyl d0 1 3. 5 959. Mixed secondary Ortho... 3.5 805.

and tertiary amyl. Pro 1 1 Para... 3. 5 80,5. Tertiary hexyl... 3.5 1,036. Octyl 3.5 1,190. Nonyl 3. 5 1, 2 7. Decyl 3.5 1, 344. Dodecyl 3. '51,498. Tertiary butyl. 3.5 945.

Tertiary amyl 3. 5 1, 022. Nonyl L 3. 5 1, 330. 'Tertiary butyl 3. 51,071.

a. 5 1,143. Nonyl 3. 5 1, 450. Tertiary butyl. 3. 5 1, 008.

20a Tertiary amyl 3.5 1,085. 21a Nonyl 3. 5 1, 393. 22a Tertiary butyl.4.2 996.

Tertiary amyl 4. 2 1, 083. onyl v 4.2 1,430. Tertiary butyl. 428 1,094.Tertiary amy-L, 4.8 1,189. on 4.8 1,570, '1ertiary amy I 1. 5 604.Cyclo-hexyL. ,7 1.5 exyl 1. 6 653 :l A E (c i j s qial RI! I derived nfrom- Acetalde- 1.

4, :PARTIS As has been pointed out previously the amine herein employedas a reactant is a basic hydroxylated secondary monoa rnine whosecomposition is indicated thus:

' v RI NH n V R'/ V n 1 V in which R represents a monovalent alkyl,alicyclic, ary'lalkyl radical which may be heterocyclic in a fewinstances as in a'seeondary amine derived from furfurylamine by.reaction of ethylene oxide or propyleneoxide. Furthermore, at least oneof the radicals designated by R must have at least one, hydroxylradical. A large number of secondary amines are available and may besuitably employed as reactants for' the present purpose. Among others,one may employ diethanolamine, methyl ethanolamine, dipropanolarnine andethylpr opanolamine, Other suitable, secondarynamines are obtained,'ofcourse, by

taking any suitable primary amine, such as'an alkylamine, anarylalkylamine, or an a'licyclic amine, and treating the amine withonemole of an oxyalkylating agent, such as ethylene oxide, propyleneoxide, butylene 'oxide, glycide, or methylglycide; Suitable pri maryamines which can' be'so converted into secondary amines, include butylamine; amylamine, hexylamine, higher molecular weight amines derivedfrom fatty acids, cyclohexylamine, benzyl amine, furfurylamine, etc. Inother instances secondary amines whichhave at least one hydroxyl radicalcan be treated similarly with an oxyalkylating agent, or, for thatmatter, withan alkylating agent such as benzylchloride, esters ofchloracetic acid, alkyl bromides, dimethylsulfate, esters of sulfonicacid, etc., so as to convert the I primary amineinto a secondary amine.Among others,

' such amines include 2 amino lbutanol, 2-amino-2- .which have not onlya hydroxyl group'but also one or more divalent oxygen linkages aspart ofan ether radical. The preparation of such amines or suitable reactantsfor preparing them has'been described in the literature, andparticularly in two United States patents, to wit, U. S.

, Patents Nos. 2,325,514 dated July 27, 1943 to Hester, V

The

and 2,355,337 dated August 8, 1944 to Spence.

latter patent describes typical haloalkyl ethers s uch as CHsO CiHtClCHI-CH2 Such haloalkylethers can be reacted with ammonia or with aprimary amine, such as ethanolamine, propanolamine, monoglycerylarnine,etc., to produce a secondary amine in which there is not only presentahydroxylradi cal but a repetitious ether linkage.

formulas:

(CaHnOCfiHLOCzHA) 7 es HOC2Il4 cannooznioczntoosnt) \NH Homn;ciHvocngonwrn)ownawncm),

7 3002114 (CHQOCHICHZCHBCHQCHZCHQ) 7 I V Ho oirn or comparable compoundshave two hydroxylated groupa of different lengths as in 110011101120cHzcnto 01120112) Other examples of suitable amines includealpha-methylbenzylamine and monoethanolamine; also amines obtained bytreating cyclohexylmethylamine with one mole of an oxyalkylating agent,aspreviously described; betaethylhexyl-butanolamine, diglycerylamine,etc. Another type of amine which is of particularrinterest because .itincludes a very definite hydrophile group includes sugar aminesfsuch asglucamine,galactamine and fructamine, such as, N-hydroxyethylg'lucamine,N-hydroxyethylgalat; amine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by HO.GHz.(lJ.CHaOH N NEn0.oHz.t :.cn2on CH3 (3H3 cmt rcmon CHaLCHaOH See, also, correspondinghydroxylated amines which can be obtained from rosin or similar rawmaterials and de scribed in U, S. Patent No. 2,510,063, dated June 6,1950, to Bried. Still other examples are illustrated by treatment ofcertain secondaryarnines such asthe followf ing, with a mole of anoxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine,phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxylgroup and a single basic amino nitrogen atom can be obtained from anysuitable alcohol or the like'by reaction with a reagent" which containsan epoxide' group and a secondary amine group. Such re-' actants aredescribed, for example, inU. S. Patents Nos.

1,977,251 and l,977,253,'both dated October 16, 1934, to

Stallmann. Among the reactants described in said latter patent are thefollowing:

CHz- -CHCHNHCH3 e I CHr-CHCHaNH-CH:CH:OH 6/ G CHQ-Qng-NH-GHP(enorn ornon0 I i l V Compounds'can be readily obtained which are exemplified by thefollowing gaunt PART 6 The products obtained by the herein describedprocesses represent cogeneric mixtures which are the result 'of acondensation reaction or reactions. Since the resin molecule cannot bedefined satisfactorily by formula, although it may be so illustrated inan idealized simplification, it is difiicult to actually depict thefinal product of the cogeneric mixture except in terms of the processitself.

"Previous reference has been made to the fact that the procedure hereinemployed is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or .in the manufacture of a phenol-amine-aldehyde resin;or else from a particularly selected resin and an amine and formaldehydein the manner described in Bruson Patent No. 2,031,557 in order toobtain a heatreactive resin. Since the condensation products obtainedare not heat-convertible and since manufacture is not restricted to asingle phase system, and since temperatures up to 150 C. or thereaboutsmay be employed, it is obvious that the procedure becomes comparativelysimple. Indeed, perhaps no description is necessary over and above whathas been said previously, in light of subsequent examples. However, forpurpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early or low temperature stage of reaction ifemployed as subsequently described; in fact, usually it is apt to be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, we have found it convenient to use a solvent andparticularly one which can be removed readily at a comparativelymoderate temperature, for instance, at 150 C. A suitable solvent isusually benzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are notsoluble except in oxygenated solvents or mixtures containing'suchsolvents are not here included as raw materials. The reaction can beconducted in such a way that the initial reaction, and perhaps the bulkof the reaction, takes place in a polyphase system. However, ifdesirable, one can use an oxygenated solvent such as a low-boilingalcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use a comparatively nonvolatile solvent such asdioxane or the diethyl-et'he'r of ethyleneglycol. One can also use amixture of benzene or xylene and such oxygenated solvents. Note that theuse of such oxygenated solvent is not required in the sense that it isnot necessary touse an initial resin which is soluble only in anoxygenated solvent as just noted, and it is not necessary to have asingle phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercialproduct which is approximately 37%, or it may be diluted down to about30% formaldehyde. However, paraformaldehyde'can be used but his morediflicult perhaps to add a solid material instead of the liquid solutionand, everything else being equal, the latter is apt to be moreeconomical. In any event, water is present as water of reaction. If thesolvent is completely removed at the end of the process, no problem isinvolved if the material is used for any subsequent reaction. However,if the reaction mass is going to be subjected to some further reactionwhere the solvent may be objectionable as in the case of ethyl orhexylalcohol, and if there is to be subsequent oxyalkylation, then,obviously, the alcohol should not be used or else it should be removed.The fact that an oxygenated solvent need not be employed, of course, isan advantage for reasons stated.

Another factbr, as far as the selection of solvent gees is whether ornot the cogeneric mixture obtained at the end or the reaction is to beused as such or in the salt form. The cogene'ric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete removal. Even if one startswith a resin which is almost water-white in color, the products obtainedare almost invariably a dark red in color or at least a red-amber, orsome color wl'iich includes both an amber component and a reddishcomponent. By and large, the melting point is apt to be lower and theproducts may be more sticky and more tacky than the original resinitself. Depending on theresin selected and onthe amine selected thecondensation product or reaction inass on a solvent-free basis maybehard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may beWater-insoluble, or water dispe'rsibl'e, or water-soluble, or'close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a 5% solution of hydrochloric acid, acetic acid, hydroxyaceticacid,'etc. One also may convert the finished product into salts by simpladding a stoichiomet'ric amount "of any selected acid and removing anywater present by refluxing with benzene 'or the like. In fact, theselection 'of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform. V K In the next succeeding paragraph 'it is pointed out thatfrequently it is convenient to'eliminate all solvent, using atemperature of not over C. and employing vacuum, ifrequired. Thisapplies, of course, only to those circumstances where it is desirable ornecessary to remove the solvent. Petroleum solvents, aromatic solvents,etc. can b'e u'sed. The selection of solvent, such as benzene, xylene,or the like, depends primarily on cost, i. e., the use of the mosteconomicalsolvent and also on three other factors, two of which havebeen previously mentioned; (a) is the solvent to remain in the, reactionmass without removal? ('b) isthe reaction mass 'to be subjected tofurther reaction in which the solventffor instance, an alcohol, eitherlow boiling or high boiling, might interfere as in the case ofoxyalkylation? and the third "factor is this, '(c) is an effort to bemade to purify the reaction mass by the usual procedure as, for example,a water-'washto remove any unreacted 16w molal soluble amine, ifemployed and present after reaction? Such procedures are well known and,needless to say,-'certain solvents are more suitable thanothe'rs.Everythingelse beingequal, We have found xylene the most satisfactorysolvent.

We have found no particular advantage in using a low temperature in theearly stage of the reaction because, and for reasons explained, this isnot necessary although it does apply in some other procedures that, in ageneral way, bear some similarity tothe present procedure. There is noobjectionjo'f course, to giving the reaction an-oppo'rtunity'to proceedas far asit will at some low temperature, for instance, 30 to 40 butultimately one must employ the higher temperature in order to obtainproducts of the kind herein described. If alower temperature reaction isused initially the period is not critical, in fact, it may be anythingfroma few hours up to 24 hours. I have not foundany case where itwasnecessary or even desirable to hold the low temperature stage for morethan 24 hours. In fact, we are not convinced thereis any ad: vantage'inholding it at this stage for more than 3 or *4 hours at'the most. This,again, is a matter of-convenience largely for one reason. In heating andstirring the reactioninass there'is a tendency for formaldehyde to -belost. Thus, if the reaction can be conducted ata lower temperaturq'thenthe arnoun't of unreacted formaldehyde is decreased subsequently andmakes it easier to prevent any loss.Here,again,'thislower'temperature'is' not nece's- 23 sary by virtue ofheat convertibility as previously referred If solvents and reactants areselected so the reactants and products of reaction are mutually soluble,then agitation is required only to the extent that it helps cooling orhelps distribution of the incoming formaldehyde. This mutual solubilityis not necessary as previously pointed V out but may beconvenient undercertain circumstances.

On the other hand, if the products are not mutually soluble thenagitation should be more vigorous for the reason that reaction probablytakes place principally at the interfaces and the more vigorous theagitation the more interfacial area. The general procedure employed isinvariably the same when adding the resin and the selected solvent, suchas benzene or xylene. Refluxing should be long enough to insure that theresin added, preferably in a powdered form, is completely soluble.However, if the resin is prepared as such it may be added in solutionform, just as preparation is described in aforementioned U. S. Patent2,499,368. After the resin is in complete solution the amine is addedand stirred. Depending on the amine selected, it may or may not besoluble in the resin solution. If it is not soluble in the resinsolution it may be soluble in the aqueous formaldehyde solution. If so,the resin then will dissolve in the formaldehyde solution as added, andif not, it is even possible that the initial reaction mass could be athree-phase system instead of a two-phase system although this would beextremely unusual. This solution, or mechanical mixture, if notcompletely soluble is cooled to at least the reaction temperature orsomewhat below, for example 35 C. or slightly lower, provided thisinitial low temperature stage is employed. The formaldehyde is thenadded in a suitable form. For reasons pointed out we prefer to use asolution and whether to use a commercial 37% concentration is simply amatter of choice. In large scale manufacturing there may be someadvantage in using a 30% solution of formaldehyde but apparently this isnot true on a small laboratory scale or pilot plant scale. 30%formaldehyde may tend to decrease any formaldehyde loss or make iteasier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldee hyde losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difficulties areinvolved. We have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as one can reasonably expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C., for 4 or hours, or at the most, up to -24 hours, we thencomplete the reaction by raising the temperature up to 150 C., orthereabouts as required. The initial low temperature procedure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature we use aphase-separating trap and subject the mixture to reflux condensationuntil the water of reaction and the water of solution of theformaldehyde is eliminated. We then permit the temperature to rise tosomewhere about 100 C., and generally slightly above 100 C., and below150 C., by eliminating the solvent or part of the solvent so thereaction mass stays within this predetermined range. This period ofheating and refluxing, after the water is eliminated, is continued untilthe reaction mass is homogeneous and then for one to three hours longer.The removal of the solvents is conducted in a conventional manner in thesame way as the removal of solvents in resin manufacture as described inaforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we haveinvariably employed approximately one mole of the resin based on themolecular weight of the resin molecule, 2 moles of the secondary amineand 2 moles of formaldehyde. In some instances we have added a trace ofcaustic as'an added catalyst but have found no particular advantage inthis. In other cases we have used a 'slight' excess of formaldehyde and,again, have not found any particular advantage in this. In other caseswe have used a slight excess of amine and, again, have not found anyparticular advantage in so doing. Whenever feasible We have checked thecompleteness of reaction in the usual ways, including the amount ofwater of reaction, molecular weight, and particularly in some instanceshave checked whetheror not the end-product showed surfaceactivity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of unreacted amine, if any is present, is another index. 7

In light of what has been said previously, little more need be said asto the actual procedure employed for the preparation of the hereindescribed condensation produc'ts. The following example will serve byway of illustration.

Example 1b The phenol-aldehyde. resin is the one that has beenidentified previously as Example2a. It was obtained from a para-tertiarybutylphenol and formaldehydel The resin was prepared using an acidcatalyst which was completely neutralized at the end of the reaction.The molecular weight of the resin was 882.5. This corresponded to anaverage of about 3 /2 phenolic nuclei, as the value for n which excludesthe 2 external nuclei, i. e., the resin'was largely a mixture having 3nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overallnuclei. The resin so obtained in a neutral state had a light ambercolor. 7

882 grams of the resin identified as 2a preceding were powdered andmixed with-700 grams of xylene. The mixture was refluxed until solutionwas complete. .It was then adjusted to approximately 30 to 35 C. and 210grams of diethanolamine added. The mixture was stirred vigorously andformaldehyde added slowly. The

formaldehyde used was a 37% solution. and 160 grams ing trap was set soas to eliminate all water of solution and reaction. After the water waseliminated part of the xylene was removed until the temperature reachedabout 150 C. The mass was kept at this higher temperature for about 3%hours and reaction stopped. During this time any additional water, whichwas probably water of reaction which had formed, was eliminated by meansof the trap. The residual xylene was permitted to stay in the cogenericmixture. A small amount of the sample was heated on a water bath toremove the excess xylene and the residual material'was dark red in'color and had the consistency of a sticky fluid or a tacky resin. Theoverall reaction time was a'little over 30 hours. In other instances ithas varied from approximately 24 to 36 hours? The time can be reduced bycutting the low temperature period to about 3 to 6 hours.

Note that in TableIV fol-lowing there are a large number of addedexamples illustrating the same procedure. In each case the initialmixture was stirred and held at a fairly low temperature. (30 to 40 C.)for a period of several. hours. Then refluxing was employed until theodor'of formaldehyde disappeared. After the odor of formaldehydedisappeared the phase-separating trap was employed to separate out allthe water, both the solution a 26 pointed out in detail elsewhereHowever, in many instances the derivatives obtained by oxyalkylation areeven more valuable and from such standpoint the herein describedproducts may be considered as valuable intermediates.

Subsequent oxyalkylation involves the use of and condensation. After allthe water had been separated ethylene oxide, propylene oxide, butyleneoxide, glycide, enough Xylene was taken out to have the final productreetc. Such oxyalkylating agents are monoepoxides as difflux for severalhours somewhere in-the range of 145 to erentiated from polyepoxldes. 150C., or thereabouts. Usually the mixture yielded a 7 It becomes apparentthat if the product obtained is clear solution by the time the bulk ofthe Water, or all of 10 to be treated subsequently with a monoepoxidewhich the water, had been removed. may require a pressure vessel as inthe case of ethylene Note that as pointed out previously, this procedureis oxide, it is convenient to use the same reaction vessel illustratedby 24 examplesinTable IV. in both instances. In other words, the 2 molesof the TABLE IV Strength of Reac- Reac- Max. Ex Resin 'Amt., formal-Solvent used tion tion dis.- No used grs. Amine used and amount dehydeand amt. temam, time, till.

soln.a11d (hrs) temcp amt. 7

882 D1ethanolamiue,210g 31%, 162g.-- Xylene, 700 22-26 32 12.7 480Diethanolamine, 105 g 37%, 81 g.--. Xylene, 450 g 21-23 28 150 633...-.do .-.-.-d Xylene, 600 (5.... -22 36 145 441 Dipropanolamine, 133 g30%, g Xylene, 400 g..-. 20-23 34 146 480 .-..-do -do. Xylene, 450g-...21-23 24 141 633 --..-do ..do Xy1ene,.600g.. 21-28 24 882Ethylethanolamine, 178g 37%,162 g... Xylene, 700 g.--. 20-26 24 152 480Ethylethanolamine, 89 g 37%, 81 g Xylene, 450 g.. 24-30 28 151 633--..-do .-..-do Xylene, 600 g... 22-25 27 147 473Oyclohexylethanolamine, 143g 30%, 100 g.-. Xylene, 450 g. 21-31 31 146511 o 37%,s1 --.--do... 22-23 36 143 666 --.--do do-. .Xylene, 550g..-.20-24 27 152 CaHsOC2H4OC2H4 1312...- 2a. 441 NH, 176g .-do Xylene, 4003.... 21-25 24 HOCzH4 CaHuOCzH4OC3H4 140---- 5a....- 480 NH, 176g doXylene, 450 g.--- 20-26 26 146 HOCIHA 021150 C2H4O 02H;

150---- 9a- 595 NH,1762 dn Xylene, 550g.--- 21-27 30 147 HOCIH!HOCzHrOCzHtOCzHt v V t 1%.... 2a... 441 NH,'192g --do Xylene, 400 g..-.20-22 30 148 HOCiHl HOC2H4OCzH4OC2H4 1712---- 5a.--" 480 NH, 192 g...--.-dn ---..do" I 20-25 28 150 HOC2H4OCzH4OG7 4 I 1471..-- 511 NH, 192g--do x len mo nfl 21-24 32 149 nocirn HOOIHOC2H4OQIH4 1%.--- 2211.---49s NH,192g .-do x 1ene.45og. 22-25 32 153 HOCaH4 OHKOCzHO:

201)-.-. 2371.--- 542 NH,206g 30%,100 g..- Xyleue,500g 21-23 36 151GH:(OO:H4)5

CH:(OC:H4)3

221).-.. 2a 441 NH, 206 g ..---do Xylene, 400 g 22-23 31 146 HOCzH4230.... 2611.... 595 Decylethanolamine, 201 g 37%, 81 g.-.- Xylene,500g.... 22-27 24 145 240.... 2741.--- 391 Deey1ethano1arnme,100 g. 30%,50 g.-.- Xylene, 300g.... 21-25 26 147 "PART 7 amine-modifiedphenol-aldehyde resin condensate would The products' obtained as hereindescribed by' reactions involving amine condensates and diglycidylethers or be reacted with"a"'polyepoxide and then subsequently with amonoepoxide. In any event, if desired the polythe equivalent arevaluable for use as such. This is 75 epoxide reaction can be conductedin an ordinary reac- V awa ts-s *tiojn vessel, suchas the usual glasslaboratory equipment; This is particularly true of the kindiused forresin manufacture as described 'in a number of pat ents, as foriexample,U; S; Patent No. 2,499,365{ 7 v a Cognizance should be takerrjofoneparti'cular feature 7 connection with 'the reaction i'nvolvin'gjthe'polyepoxide and that is thi's; the amine-modified phenol-aldehydefre'sincondensate is invariably basic and thus one need not add the usual,catalysts which are used to promote such reactions. Generallyjspeaking.the reactionwill'proceed at "catalyst at all. a 7 V, Employingpolyepoxid'es' in combination with a nona satisfactory rate,undersuitabl'e conditions without .any

basic reactant the usual catalysts include alkaline ma terials such ascaustic soda, caustic i'po'tashgi'sodiumf methylate,'j:etc. Other:catalysts. maybe, aeidicfin nature 7 and are ofthekindaclialtatfzter,izedfny, iron and tinchloride;

Furthermore, insoluble catalysts such as clays'oii specially I preparedminer lcatalystsf have been. used. ltfor ny generally employedwould-vbe'l%- or 2%.. It goes without saying than-thereaction can takeplace inl an inert solvent i. e., on e',th atis nObOXYtilkYl al-i jnon-susceptible, Generally speaking; this; is most con;

veniently an aromatic solvent such as xylene or a higher 'boilingcoaltar's olventfor; else. a similar high boiling aromatic solven;obtainedtfromipetroleum; .Onecan em- .ploy an oxygenated solvent; suchas'the diethylether of ethylene glycol, or the diethylether of propyleneglycol,

' hydrocarbon solvent. The selection of the. solvent de} pends in part.on the subsequent use of the derivatives or reaction products. If the"reaction products are to be i rendered solvenfifree and itlis necessarythat the solvent.

be readily removed as, for exampl'e; by-the use'ofa vacuurni,

distillation, thus xylene or an aromatic petroleum will -ated solventand then? shaken with 5% gluconic acid it serve. If the product is goingto be subjectedt o oxyalkylation subsequently, then the solventsh'ouldbe one which isnot oxyalkyladon-susceptible.' It easyenough toselecta suitable solvent if required in any instance but,

everything else being equal, the solvent chosen should be themosteconomical one. i V

' 7 Erdmplef'llC i or similar etherspeither alone or in combination witha f of-whathas been said. previously and in effect is a pro- The productwas obtained by reaction between the diepoxide previously designated asdiepoxide 3A, and condensate 2b. 'Condensatelbrwasobtained from resin5a.

.Resin 5a in turn was obtained from tertiary amylphenol andformaldehyde. Condensate 2b employed as reactants resin 5a anddiethanolamine. The amount of resin employe d was grams; theqamount' ofdiethanolamine J V V employed was 105 grams, and the amount of"3.7'%formaldehyde employed was 81 grams, ancllthe amount of solvent (xylene).employed was 450 grams. been described previously.

to a solution. In this particular instance, and in practically'all theothers which appear in the subsequent All' this has The solution of thecondensate in xylenewas adjusted table, the examples are characterizedbythe fact that no V V V alkaline catalyst was added. The reason ofcourse, that thecondensate'as such is' strongly basic. l t-desired,asmall amount of an alkaline catalystcould'; bejadd'ed,

V such a finely powdered causticsoda, sodium methylateg If such alkalinecatalyst is added it may speed up 'the reaction'but it also maycause anundesirablefreac tion, such as thepolymerization of a dieuoxide.

.In any event, 119,; grams of the condensate. dissolved in approximatelyan equal amount of xylene were stirred and heated to C., and 17 grams ofdiepoxide' pre viously identified as 3 A and dissolved in an equalweight of xylene wereadded'd'ropwi'se-.. .An. initialaddition'ofi 1 thexylene solution carried the temperature to about- V108 C The remainderfithe; d'iepoxide was added in approximately an hours time. During thisperiod of;

was withdrawn and, the xylene evaporated on a hot plate in order toexaminethe physical properties-f Thematerial was a dark red viscoussemi-solid. It was insoluble in'water, it was insoluble in a. 5%gluconic acid solution but was soluble, in xylene and particularly in a;mixture of 80% xylene and 20% methanol; 'However, if the material wasdissolved in an oxygen:

showed adefinite tendency to disperseysuspend or form a sol, andparticularly in a'xylene-methanol mixed sol-' vent as previouslydescribed, with or without the further addition of a little acetone. 7 a

The procedure employed ofcourser is siinplein light cedure similar tothat employed in the use of glycide or methylglycide asoxyalk-ylatingagents. See,,for example, 7

50... Part. 1. of: U. S;. Patent No. 2,602,062? dated Iuly l, 1952',

"TABLE v Con- 'lime' V .'E x., den: ,Agut ,Hlep- Amt. Xy1ene, Molar: of'reac- Max. r V I 1 V No. sate grs'. oxide gts. grs. ratio tion, temp,@0101 and'physlcal state 7 used I used hrs. I G;

- 119 3A 17 136 2:1 5' r 180 Dark viscous semi-solid. an e 17 142 2:1; 57 Do. 7

108 3A 17 125 2:1 5, Do. V r 116 3A 17 133 2:1 5. V 180 D0. 126 3A' 17143 2:1 5 190 7 D0. i 15:1. 3A. 17. 7 181 2:1 6' 180, Dank-solid mass;

12.6, 3A1 17 14B 2 :1 6 .190. Do. 143 3A 17' 160 2:1 6 190; 7 Do. 140*3A 17" 1'57 2:1 .6 196 Do: 152: "3A. 17 169 2:1 6 190 Do.

TA BLE VI Con- Time Ex den- Amt, Diep- Amt, Xylene, Molar of reac- Max.N sate grs. oxide grs. grs. ratio tion, temp, Color and physical stateused used hrs. C.

119 B1 27.5 p 146. 2:1 6 185 Dark viscous semi-solid. 125 B1 27. 5 152.5 2:1 7 188 Do. 108 B1 27. 5 185.5 2:1 6 180 D0. 116 B1 27. 5 143. 5 2:16 182 Do. 126 B1 27. 5 153. 5 2:1 8 185 Do. 164 B1 27. 5 191. 5 2:1. 8190 Dark solid mass. 126 B1 27. 5 153. 5 2:1 7 180 Do. 143 B1 27. 5 170.5 2:1 8 184 Do. 140 B1 27.5 167. 5 2:1 8 185 Do. 152 B1 27.6 179. 5 2:18 190 Do.

Solubility in regard to all these compounds was substantially similar tothat which was described in Example 10.

TABLE VII Probable Resin con- Probable Amt. of Amt. of number of Ex. No.densate molee. wt. product, solvent, hydroxyls used reaction grs. grs.per moleproduct cule TABLE VIII Probable Resin con- Probable Amt. ofAmt. of number of Ex. No. densate melee. wt. product. solvent, hydroxylsused reaction grs. grs. per moleproduct cule At this point it may bedesirable to direct attention to two facts, the first being that we areaware that other diepoxides free from an aromatic radical as, forexample, epoXides derived from ethylene glycol, glycerine, or the like,such as the following:

H HHHHH H may be employed to replace the diepoxides herein described.However, such derivatives are not included as part of the instantinvention.

At times we have found a tendency [for an insoluble mass to form or atleast to obtain incipient cross-linking or gelling even when the molalratio is in order of 2 moles of resin to one of diepoxide. We have foundthis can be avoided by any one of the following procedures or theirequivalent. Dilute the resin or the diepoxide, or both, with an inertsolvent, such as Xylene or the like. In some instances an oxygenatedsolvent, such as the diethyl ether of ethyleneglycol may beemployed.Another procedure which is helpful is to reduce the amount of catalystused, or reduce the temperature of reaction by adding a small amount ofinitially lower boiling solvent such as benzene, oruse benzene entirely.Also, we have-found it desirable at times to use slightly less thanapparently the theoretical amount of diepoxide, for instance 90% to 95%instead of 100%.

PART '8 Conventional demulsifying agents employed in the treatment ofoil field emulsions are used as such, or after dilution with anysuitable solvent, such as water, pc-

25 troleum hydrocarbons, such as benzene, toluene, xylene,

tar acid oil, resol, anthracene oil, etc. Alcohols, particularlyaliphatic alcohols, such as methyl alcohol, ethyl alcohol, denaturedalcohol, propyl alcohol, butyl alcohol, hexyl alcohol, .octyl alcohol,etc., may beemployed as diluents. Miscellaneous solvents such as Ipineoil, carbon tetrachloride, sulfur dioxide extract obtained in therefining of petroleum, etc., may be employed as diluents. Similarly, thematerial or materials employed as the demulsifying agent of our processmay be admixed with one or more of the solvents customarily used inconnection with conventional dernulsifying agents. Moreover, saidmaterial or materials may be used alone or in admixture with othersuitable well-known classes of demulsify-ing agents.

It is well known that conventional demulsi'fying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oiland water-solubility. Sometimes they may be used in a form whichexhibits relatively limited oil-solubility. However, since such reagentsare frequently used in a ratio of 1 to 10,000

or 1 .to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 asin desalting practice, such an apparent insolubility in oil and water isnot significant because said reagents undoubtedly have solubility withinsuch concentrations. This same fact is true in regard to the material ormaterials employed as the demulsifying agent of our process.

In practicing the present process, the treating or demulsifying agent isused in the conventional way, well 2,626,929, dated January 27, 1953,Part 3, and reference A is made thereto for a description ofconventionalpro cedures of demulsifying, including batch, continuous,and

down-the-hole demulsi-fication, the process essentially involvingintroducing a small amount of demuls-ifier into -a large amount ofemulsion with adequate admixture with or without the application ofheat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsirier. A mixture which illustrates such combination is thefollowing:

The demulsifier of the present invention, for example, the product ofExample 20, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a polypropylatednaphthalene rnonosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulrfonic acid, 12%; p v

A high-boiling aromatic petroleum solvent, 15%; p

V 31 Isopropyl alcohol, a The above proportions are all weight percents.

Having thus described our invention, what We claim between adifunctional monohydric phenol and an alde- V hyde having not over 8carbon atoms and reactive toward saidphenol; said resin being formed inthe substantial absence of trifunct-ional phenols; said phenol being ofthe formula in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 24 carbon atoms and substituted in the 2,4,6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any group attached to the amino nitrogen atom,and (0) formaldehyde; said condensation reaction being conducted at atemperature sufiiciently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction; and with the provisothat the I resinous condensation product resulting from the process beheat-stable and oxyalkylationsusceptible; followed by (B) reacting saidresin condensate with a phenolic polyepoxide free from reactivefunctional groups other than ep oxy and hydroxyl groups andcogenericallyassociated compounds formed in the preparation "of saidpolyepoxides; said epoxides being monomers and low molal polymers notexceeding the tetra-mers; said polyepoxides being selected from theclass consisting of (aa) compounds where the phenolic nuclei aredirectly joined without an intervening bridge radical, and (bb)compounds containing a radical in which 2 phenolic nuclei are joined bya divalent radical selected from the class consisting of ;ketoneresidues formed by the elimination of the ketonic oxygen atom, andaldehyde residues obtained by the elimination of the ketonic oxygenatom, and aldehyde residues obtained by the elimination of the aldehydeoxygen atom, the divalent radical H H C C. H H

the divalent radical, the divalent sulfone radical, and the divalentmonosulfide radical -S, the divalent radical -CH2SCHz-- and the divalentdisulfide radical -'S--'S; said phenolic portion of the diepoxides beingobtained from a phenol of the structure.

having not over 18 carbon atoms;'with the further proviso that saidreactive compounds (A) and (B) be members'of the class consisting ofnon-thermosettin-g organic solvent-soluble liquids and low-meltingsolids; with the added proviso that the reaction product be amember ofthe class of solvent-soluble liquids and low-melting solids; saidreaction between (A) and (B) be conducted below the pyrolytic point ofthe reactants and the resultants of reaction; and with the final provisothat the ratio of reactants be 2 moles of the resin condensate to 1 moleof the phenolic polyepoxide.

'2. A process for breaking petroleum emulsions o-fthe water-in-oil typecharacterized by subjecting the emulsion to the act-ion of ademulsifier, said demulsifier being obtained by first (A) condensing (a)an oxyalkylationsusceptible, tusib'le, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over '6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunuctional phenols; saidphenol being of the tormula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24'carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resu'ltants ofreaction; and with the proviso that the resin ous condensation productresulting from the processbe heat-stable and oxyalkylation-susceptible;followed' by (B) react-ing phenolic epoxides being principallypolyepoxides, including phenolic tdiepoxides; said epoxides being freefrom reactive functional groups other than epoxy and hydroxyl groups,and including additionally cogenerical'ly associated compounds formed inthe preparation of said polyepoxides and diepoxides; said epoxides beingmonomers and low molar polymers not exceeding the tetrarner; saidepoxides being selected from the class consisting of (aa) compoundswhere the phenolic nuclei are directly joined without an interveningradical, and (bb) compounds containing a radical in which 2 phenolicnuclei are joined by a divalent radical selected from the classconsisting of ketone residues formed by the elimination of the ketonicoxygen atom, and aldehyde residues obtained by the elimination of thealdehydic oxygen atom, the divalent radical the divalent radical, the,divalent 'sulfonic radical, and the divalent radical -CH2S CH2, and thedivalent disulfide radical S'S'; said phenolic portion of thediepoxidebeing obtained from a phenol of the structure II! II R in whichR, R", and R' represent a member of the class consisting of hydrogen andhydrocarbon substituents of the aromatic nucleus, said substituentmember having not over 18 carbon atoms; with the further proviso thatsaid reactive compounds (A) and (B) be members of the class consistingof non-thermosetting organic solventsoluble liquids and low-meltingsolids; with the final proviso that the reaction product be a member ofthe class of solvent-soluble liquids and low-melting solids; and saidreaction between (A) and (B) be conducted below the pyro'ltic point ofthe reactants and resultants of reaction.

3. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier,said demulsifier being obtained by first (A) condensing (a) anoxyalkylationsusceptible, fusible, non-oxygenated organicsolvent-soluble water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being ditunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difuctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least'4 and not more than 24 carbon atoms andsubstituted in the 2, 4, 6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufiiciently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; and with the proviso that the resinous condensation productresulting from the process be heat-stable and oxyalkylation-susceptible;followed by (B) reacting a phenolic diepoxide free from reactivefunctional groups other than epoxy and hydroxyl groups, andcogenerically associated compounds formed in the preparation of saiddiepoxides; said epoxid-es being monomers and low molal polymers notexceeding the tetramers; said epoxides being selected'from the classconsisting of (aa) compounds where the phenolic nuclei are directlyjoined without an intervening bridge radicahand (bb) compoundscontaining a radical in which 2 phenolic nuclei are joined by a divalentradical selected from the class consisting of ketone residues formed bythe elimination of the ketonic oxygen atom, and aldehyde residuesobtained by the elimination of the aldehydic oxygen atom, the divalentradical the divalent radical, the divalent sulfone radical, and thedivalent monosuifide radical S, the divalent radical -CH2SCI-Ie and thedivalent disulfide radical -'s s said phenolic portion of the diepoxidebeing obtained from a phenol of thestructure in which R, R", and.R"represent a member of the class consisting of hydrogen and hydrocarbonsubstituents of the aromatic nucleus, said substituent member having notover 18 carbon atoms; with the further proviso that said reactivecompounds (A) and (B) be members of the class consisting ofnon-thermosetting organic solvent-soluble liquids and low-meltingsolids; with the final proviso that the reaction product be a member ofthe class of solventsoluble liquids and low-melting solids; and saidreaction between (A) and (B) be conducted below the pyrolytic point ofthe reactants and the resultants of reaction.

' 4. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier,said demulsifier being ob tained by first (A) condensing (a) anoxyalkylationsusceptible, fusible, vnonoxygenated organicsolvent-soluble water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreact-ion between a difun-ctional monohydric phenol and an aldehydehaving not over 8 carbon atoms and reactive toward said phenol; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2, 4, 6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resulants ofreaction; and with the proviso that the resinous condensation productresulting from the process be heat-stable and oxyalkylation-susceptible;followed by (B) reacting a phenolic diepoxide free from reactivefunctional groups other than epoxy and hydroxyl groups, andcogenerically associated compounds formed in the preparation of saiddiepoxides; said epoxides being selected from the class consisting of(aa) compounds Where the phenolic nuclei are directly joined without anintervening bridge radical, and (bb) compounds containing a radical inwhich 2 phenolic nuclei are joined by a divalent radical selected fromthe class consisting of ketone residues formed by the elimination of theketone residues formed by the elimination of the ketonic oxygen atom,and aldehyde residues obtained by the elimination of the keton'ic oxygenatom, and aldehyde residues obtained by the elimination of the aldehydicoxygen atoms, the divalent radical H H G Q H H a the divalent radical,the divalent sulfone radical, and the divalent monosulfide radical -S,the divalent radical -CH2SCH2- and the divalent disulfide radical SSsaid phenolic the structure 'radical, and (bb) compounds containing aradical in 2,771,436 m m t 354., ,36. l r in which RQR, and R' representa member of the class a radical; the, divalnt' sulfon e radical, and thedivalent consisting for hydrogen and hydrocarbon substituents ofmonosulfide radical S-, thedivalentradical p k H the aromatic nucleus,said substituent member having not I over 18 carbon atoms; the ratio ofreactant (A) to reactant' (B) being at least sufficient so there isavailable at 5 and the divalent disulfide radical said phenolic portionof the diepoxide being obtained from a phenol least one active hydrogenin (A) for each oxirane ring in 4 of the structure the diepoxidereactant (B); with the further proviso that said reactive Compounds (A)and (B) the members'of the class consisting of non-thermosetting organicsolventsoluble liquids and low-melting solids; with the final provisothat the reaction product be a member of the class Hie" ofsolventcoluble liquids and low-melting solids; and said reaction between(A) and (B) be conducted below the N H m pyrolytic point of thereactants and the resultants of reao. wh'lch i: R and R represent amembFr of the 1 7 class consisting of hydrogen and hydro-substltuents ofthe aromatic nucleus, said substituent member having not over 18 carbonatoms, the ratio of reactant (A) to reacttion. I

5. Afprocess, for breaking petroleum emulsions of the ant (B) being atleast s'ufficient so there is available at least one active hydrogen in(A) for each oxirane ring in waterin-oil type characterized bysubjecting the emulsion to theaction of a demulsifier, said demulsifierbeing 0b- 20 the diepoxide reactant (B); with the further proviso thatsaid reactive compounds (A) and (B) be members of tained by first (A)condensing (a) an oxyalkylationthe class consisting of non-thermosettingorganic'solventsusceptible, fusible, nonoxygenated organicsolvent-soluble water-insoluble, low-stage phenol-aldehyde resinhavsoluble liquids and low-melting solids; with the final proviso thatthe reaction product be a member of the class ing an average molecularweight corresponding to at of solvent-soluble liquids and low-meltingsolids; and said least 3 and not over 6 phenolic nuclei per resinmolecule;

said resin being difu-nctional only in regard to methylolreactionbetween (A) and (Blbeing conducted below the pyrolytic point of thereactants and the resultants of forming reactivity; said resin beingderived by reaction between a difunctional monohydric phenol and analdereaction. p

6. A process for breaking petroleum emulsions of the hyde having notover 8 carbon atoms and reactive toward said phenol; said resin beingformed in the substantial absence of trifunctional phenols; said phenolbeing of the formula water-in-o il type characterized by sub1ect1ng theemulsion v to the action of a demulsifier, salddemulsifier being 0b- 03a tained by first .(A) condensing (a) an oxyalkylationsusceptible,fusible, non-oxygenated organic solvent-solu- R ble, water-insoluble,low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said'resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between adifunctional monohydric phenol and an aldehyde having not over 8 carbonatoms and reactive toward said phenol; said'resin being formed in thesubstantial absence of trifunctional phenols; said phenol being of theformula in which R is an aliphatic hydrocarbon radical having at least 4and not more than 24 carbon atoms and substituted in the 2, 4, 6position; (b) a basic hydroxylated secondary monoamine having not morethan 32 carbon atoms in any 40 group attached to the amino nitrogenatom, and (c) formaldehyde; said condensation reaction being conductedat a temperature sufiiciently high to eliminate water and below thepyrolytic point of the reactants and resultants of reaction; and withthe proviso that the resinous con-' V densation product resulting fromthe process be heatstable and oxyalkylation-susceptible; followed by (B)reactinga phenolic diepoxide free from reactive functional 7 groupsother than epoxy and hydroxyl groups, and coin which R"" is an aliphatichydrocarbon radical having generically associated compounds formed inthe preparaat least 4 and not more than 24 carbon atoms and subtion ofsaid diepoxides, including monoepoxides; said costituted in the 2,4,6position; (b) a basic hydroxylated generically associated compoundscontaining an average secondary monoamine having not more than 32 carbonof more than one epoxide group per molecule; said epoxatoms in any groupattached to the amino nitrogen atom, ides being monomers and low molalpolymers not exceedand (0) formaldehyde; said condensation reactionbeing ing. the tetramers; said epoxides being selected from theconducted at a temperature sufliciently high to eliminate classconsisting of (aa) compounds where the phenolic water and below thepyrolytic point of the reactants and nuclei are directly joinedwi thoutan, intervening bridge resultants of reaction; and with the proviso thatthe resinous condensation product resulting from the process be which 2phenolic nuclei are joined by a divalent. radical heat-stable andoxyalkylation-susceptible; followed by (B) selected from the classconsisting of ketone residues reacting a member of the class consistingof (aa) comformed by the elimination of the ketonic oxygen atom, poundsof the following formula in which R represents a divalent radicalselected from the class consisting-of ketone residues formed by the andaldehyde residues obtained by tho elimination of the aldehydic oxygenatom, the divalent radical H H I I 7 elimination of the ketonie oxygenatom and aldehyde 7 g-g- I residues obtained by the elimination of thealdehydic t oxygen atom, the divalent radical the divalent and thedivalent disulfide radical -SS; and R is the divalent radical obtainedby the elimination of a hydroxyl hydrogen atom and a nuclear hydrogenatom from the phenol the divalent i 1,, RI! I in which R, R", and Rrepresents a member of the class consisting of hydrogen and hydrocarbonsubstituents of the aromatic nucleus, said substituent member having notover 18 carbon atoms; the ratio of reactant (A) to reactant (B) being atleast suflicient so there is available at least one active hydrogen in(A) for each oxirane ring in the diepoxide reactant (B); n represents aninteger selected from the class of zero and 1, and n represents a wholenumber not greater than 3; and (bb) cogenerically associated compoundsformed in the preparation of (aa) preceding, including monoepoxides;with the further proviso that said reactive compounds (A) and (B) bemembers of the class consisting of nonthermosetting organicsolvent-soluble liquids and lowmelting solids; with the final provisothat the reaction product be a member of the class of solvent-solubleliquids and low-melting solids; and said reaction between (A) and (B)being conducted below the pyrolytic point of the reactants and theresultants of reaction.

7. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifier,said demulsifier being obtained by first (A) condensing (a).anoxyalkylationsusceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R"" is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (c) formaldehyde; said condensationreaction being conducted at a temperature suti'iciently high toeliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by (B) reacting a member of theclass consisting of (aa) compounds of the following formula wherein R isan aliphatic hydrocarbon bridge, each n 38 independently has one of thevalues 0 to 1', and Ri is an alkyl radical containing from 1 to 12carbon atoms, and (bb) cogenerically associated compounds formed in thepreparation of (aa) preceding, including monoepoxides; with the provisothat (B) consist principally of the men: orner as distinguished fromother cogeners; the ratio of reactant (A) to reactant (B) being. atleast sufi'lcient so there is available at least one active hydrogen in(A) for each oxirane ring in the diepoxide reactant (B); with thefurther proviso that said reactive compounds (A) and (B) be members ofthe class consisting of nonthermosetting organic solvent-soluble liquidsand low melting solids; with the final proviso that the reaction productbe a member of the class of solvent-soluble liquids and low-meltingsolids; and said reaction. between (A) and (B) being conducted below thepyrolytic point of the reactants and the resultants of reaction.

8. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting theemulsion to the action of a demulsifier,said demulsifier being obtained by first (A) condensing (a) anoxyalkyla-tion-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average'molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difuncti'onal monohydr'ic phenol and an aldehydehaving not over 8 carbon atoms and reactive toward said phenol; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature suflicient-ly high toeliminate Water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by (B) reacting a member of theclass consisting of (aa) compounds of the following formula and (bb)cogenerically associated compounds formed in the preparation of (aa)preceding, including monoepoxides; with the proviso that (B) consistprincipally of the monomer as distinguished from other cogeners; theratio of reactant (a) to reactant (B) being at least suificient so thereis available at least one active hydrogen in (A) for each oxirane ringin the diepoxide reactant (B); with the further proviso that saidreactive compounds (A) and (B) be members of the clas consisting ofnon-therm-osetting organic solvent-soluble liquids and low-meltingsolids; with the final proviso that the reaction product be a member ofthe class of solvent-soluble liquids and low-melting solids; and saidreaction between (A) and (B) being conducted below the pyrolytic point'of the reactants and the resultants of reaction.

9. The process of claim 8 wherein the precursory phenol contains atleast 4 and not over 14 carbon atoms in the substituent radical.

10. The process of claim 8 wherein the precursory phenol contains atleast 4 and not over 14 carbon atoms in the substituent radical and theprecursory aldehyde is 12 The process of claim 2, with the proviso thatthe hydrophile properties of the product of, the condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro' base as is, (b) the free base, and (c) the salt of gluconicacid, in an equal weight of xylene are suificient to produce an emulsionwhen said xylene solution is shaken vigorously with 1 to 3 volumes ofwater; I V

13, The process of claim 3, "with the proviso that the hydrophileproperties of the product-of the condensation reaction employed in theform of a' member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of gluconic acid, in an equal weightof xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water. 7 v

14. The process of claim 4, with the proviso that the hydrophileproperties of the product of the condensation reaction employed in thefiorm of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of gluconic acid, in an equal weightof xylene are suflicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water. i t

15. The process of claim 5, with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of gluconic acid, in an equal weightof xylene are sufficient to produce an emulsion when said Xylenesolution is shaken vigorously with 1 to 3 volumes of water. r

,16. The process of claim 6, with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theformof a member of the class consisting of (a) the anhydro base as is,-(b) the free base, and (c) the salt of gluconic acid, in an equal weightof xylene are sufficient to produce an emulsion when said Xylenesolution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 7, with the proviso that the hydrophilepropertiesof the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of gluconic acid, in an equal weightof xylene are suflicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 8, with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of gluconic acid, in an equal Weightof xylene are sufiicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

19. The process of claim 9, with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base,

and (c) the salt of gluconic acid, in an equal weight of of water. 7

References Cited in the file of this patent I UNITED STATES PATENTS2,098,869 Harmon et al Nov. 9, 1937 2,191,943 Russell et al Feb. 27,1940 2,457,634 Bond et Val. Dec. 28, 1948 2,494,295 G-reenlee Jan. 10,1950 2,589,198 Monson' Mar. 11, 1952 2,679,485 De Groote May 25, 19542,695,888 De Groote Nov. 30, 1954

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER,SAID DEMULSIFIER BEING OBTAINED BY FIRST (A) CONDENSING (A) ANOXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANICSOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA